Short Self‐Assembling Peptides Are Able to Bind to Copper and Activate Oxygen

Abstract

We have shown that de novo designed peptides self-assemble in the presence of copper to create supramolecular assemblies capable of oxidation of dimethoxyphenol in the presence of dioxygen. Formation of the supramolecular assembly, akin to a protein fold, is critical for productive catalysis as the peptides possessing the same functional groups, but lacking the ability to self-assemble do not catalyze substrate oxidation. The ease with which we have discovered robust and productive oxygen activation catalysts suggests that these prion-like assemblies might have served as intermediates in evolution of enzymatic function and opens the path for development of new catalyst nanomaterials.

Copper‐Coordinated Histidyl Bolaamphiphile Assembly as an Oxidative Catalyst: Coordination Structure and Catalytic Activity in Cyclohexane Oxidation

“…Considering the molar content of HisC7, the small number of HisC7 ligands presumably regulates the coordination of Cu 2 + ions, forming another coordination sphere around the copper center. [8,39] It was predicted that the copper species had the 1 N3O structure when the catalyst was prepared using a HisC7/Cu molar ratio of 0.75, while the 2 N2O structure would prevail for the HisC7[Cu] prepared using molar ratios of 1 or 2. [36] Note that dimeric or oligomeric copper complexes were not considered from EPR spectra because seven line hyperfine patterns originating from two copper coupling was not observable at low magnetic field (< 2300 G).…”

“…[37,38] Using the parameters determined above, the coordination environments of the Cu 2 + centers were predicted via the Blumberg-Peisach plot which correlates the EPR parameters to the coordination structures of copper centers ( Figure S3). [8,39] It was predicted that the copper species had the 1 N3O structure when the catalyst was prepared using a HisC7/Cu molar ratio of 0.75, while the 2 N2O structure would prevail for the HisC7[Cu] prepared using molar ratios of 1 or 2. Thus, it was inferred that imidazoles coordinates at the Cu 2 + ions preferentially, and then carboxylates coordinates at the Cu 2 + ions once the imidazoles are saturated.…”

“…[1][2][3] Using various supramolecular catalysts, catalytic reactions including hydrogenation, [4,5] oxidation, [6][7][8] and the aldol reaction [9][10][11] have been explored under mild conditions, which is beneficial for decreasing the energy consumption of these processes. [1][2][3] Using various supramolecular catalysts, catalytic reactions including hydrogenation, [4,5] oxidation, [6][7][8] and the aldol reaction [9][10][11] have been explored under mild conditions, which is beneficial for decreasing the energy consumption of these processes.…”

“…Supramolecular catalysts mimicking the active sites of metalloenzymes have attracted wide research interest because of their molecular design applications, relatively simple syntheses, and complex nanoscale structures. [1][2][3] Using various supramolecular catalysts, catalytic reactions including hydrogenation, [4,5] oxidation, [6][7][8] and the aldol reaction [9][10][11] have been explored under mild conditions, which is beneficial for decreasing the energy consumption of these processes. Among these reactions, oxidation of organic compounds has been widely studied because inexpensive hydrocarbons can be converted to more valuable products via oxidative catalysis in the chemical and petrochemical industries.…”

Competition versus Cooperation in Catalytic Hydrogelators for anti‐Selective Mannich Reaction

“…It also allows better cooperation and increased local concentration of the functional groups, along with added advantages, such as easier product separation and recyclability of the self‐assembled catalyst . Owing to these properties, self‐assembling catalytic hydrogelators have previously been reported to carry out transformations, such as the Henry reaction, Aldol reaction, ester hydrolysis, and oxygen activation, with enzyme‐like efficacy. However, their application in a combinatorial approach for complex multicomponent reactions for enantio‐ and diastereoselective transformations still remains to be tested.…”